KR101733369B1 - Decorative sheet, and decorative member in which same is used - Google Patents

Abstract

An object of the present invention is to provide a decorative sheet (1) having designability including an appearance and a texture (touch) including excellent finish and a good molding processability in response to a demand for thinning. The present invention relates to a decorative sheet comprising a decorative sheet (3) and a surface protective layer (5) in this order on a base sheet (2) composed of a polyester resin or a polyolefin resin and having a total thickness of 70 to 135 탆, The protective layer 5 has the concave shape 6 and the maximum depth of the concave shape 6 is 15 to 100% relative to the total thickness and is 15 占 퐉 or more, (1) wherein the ratio of the tensile elastic modulus is 1:12 to 1: 160, and the ratio of the maximum point load at 30 캜 stretching at 120 캜 and 20 캜 is 1: 1.7 to 1:30.

Description

[0001] DESCRIPTION [0002] DECORATIVE SHEET, AND DECORATIVE MEMBER IN WHICH SAME IS USED [0003]

The present invention relates to a cosmetic sheet and a makeup member using the same.

A decorative sheet is generally used for decorating interior and exterior members of a building such as a wall, a ceiling and a floor, or a window frame, a door, a railing, a mop base, a spin table, a mall, or the like (for example, refer to Patent Document 1 ). Considering that the decorative sheet is decorated with a complicated shape, the thinner the sheet, the better the processability. In terms of the environment, the concept of recycling members such as wood-based substrates, resin substrates, and the like constituting interior and exterior members of a building or a window is infiltrated to the general public, so that the recycled property is not damaged. (Thinning of the decorative sheet) is desired.

It is necessary to subject the decorative sheet to a bonding treatment such as laminating or lapping on the member (adherend), and then cutting the decorative sheet. In general, the decorative sheet may be heated by the friction during cutting. Depending on the kind of the adhesive used, the decorative sheet may be heated (warmed) during the laminating process or the lapping process, or may be heated (heated) during the V-cut process or the assembly process. It is also assumed that the decorative sheet is left in a state in which heat is left in the finish. As described above, the decorative sheet is required to be adapted to thermal characteristics in that it is assumed that the decorative sheet is handled in a heated state or a state in which heat is left at the time of processing. Vacuum forming processing is known as a method of processing a decorative sheet. At the time of vacuum forming, the decorative sheet is placed in a heated environment and also in a vacuum environment, so that the decorative sheet must be adapted to mechanical properties (strength) in addition to thermal properties. If these properties are not satisfied, peeling of the decorative sheet and member (adherend) occurs. Further, the decorative sheet may be peeled, peeled, or wrinkled, resulting in deterioration of molding processability, which greatly impairs designability of the obtained member, window, and the like.

It is also important to express the design of the appearance or texture (tactile feeling) in addition to the designability on the finished surface in which the sheet does not suffer from galling, bursting, or wrinkling, Performance. As means for expressing this designability, a method of forming a concave shape on the surface by embossing and patterning is generally employed. When the means for expressing such designability is employed, if the decorative sheet is too thin, the decorative sheet is broken at the time of embossing. Further, if the decorative sheet is too thin, the concave shape comes out to the back surface of the decorative sheet by the embossing process, so that when the decorative sheet is adhered to the member (adherend), the concave shape becomes like a distorted finish.

Further, in order to improve the adhesion between the decorative sheet and the adhesive when the decorative sheet is adhered to the member (adherend), and in order to suppress the damage to the member (adherend), an adhesive is applied to the decorative sheet . In this case, if a hot melt adhesive is used as the adhesive, the concave shape due to the embossing may become shallow or disappear depending on the constitution or material of the decorative sheet.

Japanese Patent Application Laid-Open No. 2000-326451

The decorative sheet disclosed in Patent Document 1 and used for obtaining a decorative member by a laminating process or a lapping process in a conventionally used decorative sheet is required to have an excellent molding processability in spite of being thinner, In addition, a decorative sheet having an appearance or texture with respect to texture is not yet provided. As a result, such a toilet sheet is strongly desired.

Accordingly, in view of the above problems, it is an object of the present invention to provide a decorative sheet having excellent molding processability in correspondence with a demand for thinning, and having designability including appearance, texture (touch), and the like.

The inventors of the present invention have conducted intensive studies in order to achieve the above object, and as a result, they have found that the above problems can be solved by the following invention. That is, the present invention provides the following cosmetic sheet and a cosmetic member using the same.

1. A decorative sheet comprising a base sheet composed of a polyester resin or a polyolefin resin and having a decorative layer and a surface protective layer in this order and having a total thickness of 70 to 135 占 퐉 and at least the surface protective layer having a concave shape, Wherein the maximum depth of the concave shape is 15 to 100% with respect to the total thickness and is 15 占 퐉 or more, the ratio of the tensile elastic modulus at 120 占 폚 and 20 占 폚 is 1:12 to 1: 160, Wherein the ratio of the maximum point load at 30 mm stretching is 1: 1.7 to 1:30.

2. A decorative sheet according to Item 1, further comprising a resin layer between the substrate sheet and the surface protection layer.

3. The decorative sheet according to item 1 or 2 above, wherein the base sheet is composed of a polyolefin resin.

4. The decorative sheet according to item 2 or 3 above, wherein the resin layer is composed of a polyolefin resin.

5. The decorative sheet according to any one of items 1 to 4, wherein the surface protection layer is a cured product of the ionizing radiation curable resin composition.

6. The decorative sheet according to any one of items 1 to 5, wherein the base sheet, the decorative layer, the resin layer and the surface protective layer are in this order, and the resin layer and the surface protective layer are transparent.

7. The decorative sheet according to any one of items 1 to 6, which is used for laminate processing or lapping processing.

8. A cosmetic member comprising a base sheet side surface of the decorative sheet according to any one of items 1 to 7 and an adherend bonded together with an adhesive layer interposed therebetween.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to obtain a decorative sheet having excellent molding processability and designability including appearance, texture (touch) and the like while coping with the demand for thinning.

Fig. 1 is a schematic view showing an example of a preferable constitution of the decorative sheet of the present invention. Fig.

The decorative sheet of the present invention has a decorative layer and a surface protective layer in this order on a base sheet made of a polyester resin or a polyolefin resin and has a total thickness of 70 to 135 占 퐉 and at least the surface protective layer has a concave shape , And the depth of the concave shape is 15 to 100% with respect to the total thickness, and is 15 占 퐉 or more, and the ratio of the tensile elastic modulus at 120 占 폚 and 20 占 폚 (hereinafter simply referred to as the ratio of the tensile elastic modulus Is 1:12 to 1: 160, and the ratio of the maximum point load at the time of 30 mm stretching at 120 ° C and 20 ° C (hereinafter simply referred to as the ratio of the maximum point load) is 1: 1.7 To 1:30.

Hereinafter, the configuration of the decorative sheet of the present invention will be described in detail with reference to Fig. Fig. 1 shows an example of a preferable constitution of the decorative sheet 1 of the present invention. The decorative sheet 1 shown in Fig. 1 has a decoration layer 3, a resin layer 4 and a surface protection layer 5 on a base sheet 2 in this order. The surface protection layer 5 has a concave shape 6. This concave shape 6 includes, as shown in Fig. 1, one that stays in the surface protective layer 5, one that reaches the base sheet 2, and the like.

First, properties of the total thickness, the ratio of the tensile elastic modulus, and the ratio of the maximum point load of the decorative sheet of the present invention will be described.

The total thickness of the decorative sheet of the present invention should be about 70 to 135 mu m. When the thickness is less than 70 탆, excellent thinning resistance is obtained but good scratch resistance is not obtained and protection of the decorative layer is sometimes insufficient. On the other hand, if it is thicker than 135 占 퐉, peeling (spring back) of the decorative sheet and the member occurs at the time of lapping, and excellent molding processability or design property can not be obtained. From the same viewpoint, the total thickness is preferably 75 to 125 占 퐉, more preferably 90 to 125 占 퐉.

In the decorative sheet of the present invention, the ratio of the tensile elastic modulus at 120 占 폚 and 20 占 폚 is 1:12 to 1: 160. When the ratio of the tensile elastic modulus is less than 1:12 (the tensile elastic modulus at 20 캜 is smaller), protrusions or recesses, dropouts, or the like are generated on the decorative sheet during cutting processing after lapping , And processability (cutting property) deteriorates. On the other hand, when it is larger than 1: 160 (when the tensile elastic modulus at 20 캜 is larger), the decorative sheet becomes too soft when heat is applied thereto, , The designability deteriorates. From the same viewpoint, the ratio of the tensile elastic modulus is preferably 1:20 to 1: 130, more preferably 1:30 to 1: 100, and even more preferably 1:30 to 1:75.

Here, the ratio of the tensile elastic modulus is obtained by measuring the tensile elastic modulus at 120 占 폚 and 20 占 폚, and calculating the ratio. The tensile modulus of elasticity was measured by using a tensile compression testing machine under the temperature conditions of 120 占 폚 and 20 占 폚 by preparing a decorative sheet punched with a dumbbell-shaped test piece conforming to JIS K6732 and measuring the tensile modulus at a tensile rate of 50 mm / From the first straight line portion of the tensile stress-strain curve obtained by measurement under the condition, the following equation is used.

E = Δρ / Δε

E: tensile modulus

Δρ: stress difference due to the circle average cross-sectional area between two points on the straight line

Δε: Distortion difference between two identical points

In the decorative sheet of the present invention, the ratio of the maximum point load at 30 캜 stretching at 120 캜 and 20 캜 is 1: 1.7 to 1:30. When the ratio of the maximum point load is less than 1: 1.7 (when the maximum point load at 20 캜 is smaller), the decorative sheet may have protrusions or recesses, dropouts, or the like at the time of cutting processing after lapping And the workability (machinability) deteriorates. If the ratio of the maximum point load is less than 1: 1.7, the decorative sheet is too hard to form a good concave shape, and designability is reduced. On the other hand, if it is larger than 1:30 (when the maximum point load at 20 ° C is larger), the decorative sheet becomes too soft when heat is applied, and the recessed shape is recovered by heating during lapping or other processing And the designability deteriorates. From the same viewpoint, the ratio of the maximum point load is preferably 1: 2.5 to 1:25, and more preferably 1: 5 to 1:15.

Here, the ratio of the maximum point load is obtained by measuring the maximum point load at 120 占 폚 and 20 占 폚, and calculating the ratio. The maximum point load was obtained by preparing a decorative sheet punched in the form of a dumbbell-shaped test piece conforming to JIS K6734 and measuring the tensile stress at a tensile speed of 50 mm / minute and a distance between chucks of 80 Mm. ≪ / RTI >

[Base sheet]

Next, each layer constituting the decorative sheet of the present invention will be described.

The substrate sheet in the decorative sheet of the present invention is composed of a polyester resin or a polyolefin resin. By using the base sheet made of these resins, the ratio of the tensile elastic modulus and the ratio of the maximum point load can be set within a predetermined range, and excellent moldability can be obtained with excellent molding processability.

As the polyester resin, a known polyester resin used in this field can be widely used. Examples of the polyester resin include polyethylene terephthalate (hereinafter sometimes referred to as "PET"), polybutylene terephthalate, polyethylene naphthalate, polyarylate, polycarbonate, ethylene terephthalate-isophthalate copolymer , Polyarylate, and the like. Of these, polyethylene terephthalate and polybutylene terephthalate are preferable, and polyethylene terephthalate is more preferable.

As the polyolefin resin, a known polyolefin resin used in this field can be widely used. Examples of the polyolefin resin include polyethylene (low density polyethylene, medium density polyethylene, high density polyethylene and the like), polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer and propylene-butene copolymer. Of these, polyethylene and polypropylene are preferred. A polyolefin resin is preferably used because it is a resin which can easily bring the ratio of the tensile modulus of elasticity and the ratio of the maximum point load within a predetermined range.

The thickness of the substrate sheet is preferably about 20 to 130 탆, more preferably about 30 to 100 탆, and even more preferably about 40 to 80 탆. When the thickness of the base sheet is within the above-mentioned range, the total thickness of the decorative sheet is easily adjusted within the range specified in the present invention, and superior moldability along with excellent molding processability is obtained.

It is preferable that the substrate sheet is made of a colored resin. By using the colored resin, in the case where the surface color of the member to which the decorative sheet is adhered is varied, the surface color can be favorably concealed. As a result, more excellent designability can be obtained, and the stability of the color tone of the decorative layer provided according to the purpose can be ensured.

The colorant to be used for the above purpose may be suitably selected in accordance with the use. By using a colorant, for example, the substrate sheet can be colored in colorless transparent or colorless opaque. In general, it is desirable to make the color opaque because it is necessary to conceal the surface of the member to be the adherend. Examples of the colorant include inorganic pigments such as carbon black (black), iron black, titanium white, antimony white, chrome yellow, titanium yellow, red iron oxide, red cadmium red, gold blue, cobalt blue, quinacridone red, isoindolinone yellow, phthalocyanine blue (Pearl) pigment containing flaky flakes such as titanium dioxide coated mica, basic carbonate flakes and the like, and the like are used.

The amount of the colorant to be added is usually about 1 to 50 parts by mass with respect to 100 parts by mass of the resin forming the substrate sheet.

The substrate sheet may be subjected to physical or chemical surface treatment such as oxidation or unevenness on one side or both sides of the base sheet for the purpose of enhancing the interlaminar adhesion between the base sheet and other layers and the adhesion between the base sheet and various adherends .

Examples of the oxidation method include a corona discharge treatment, a chromium oxidation treatment, a flame treatment, a hot air treatment, an ozone treatment and an ultraviolet treatment. Examples of the unevenness method include a sand blast method and a solvent treatment method. These surface treatments are appropriately selected according to the kind of the substrate, and the corona discharge treatment method is preferably used in view of the effect and the operability.

Further, a treatment such as forming a primer layer or a backside primer layer may be performed for the purpose of enhancing the interlayer adhesion between the base sheet and each layer.

An inorganic filler may be added to the base sheet, if necessary. Examples of the inorganic filler include powders of calcium carbonate, barium sulfate, clay, talc, silica (silicon dioxide) and alumina (aluminum oxide). The amount of the inorganic filler to be added is usually about 1 to 50 parts by mass based on 100 parts by mass of the resin forming the substrate sheet.

Further, various other additives such as a foaming agent, a flame retardant, a lubricant, an antioxidant, an ultraviolet absorber, a light stabilizer and the like may be blended in the base sheet, if necessary.

[Decorative floor]

The decorative layer of the decorative sheet of the present invention imparts decorative qualities to the decorative sheet of the present invention. The decorative layer may be a uniformly uniform colored layer covering the entire surface of the decorative sheet, a pattern layer formed by printing various shapes using an ink or a printing machine, or a combination thereof.

As the ink used for the decorative layer, an appropriate mixture of a colorant such as a pigment and a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent and the like is used for the binder.

The binder is not particularly limited and a curable resin such as a thermoplastic resin, a one-liquid curable resin, and a two-liquid curable resin can be used. As the thermoplastic resin, for example, a vinyl chloride / vinyl acetate copolymer resin, a vinyl chloride / vinyl acetate / acrylic copolymer resin, a chlorinated polypropylene resin, an acrylic resin, a polyester resin, a polyamide resin, , A polystyrene-based resin, a nitrocellulose-based resin, and a cellulose acetate-based resin. As the thermosetting resin, for example, a polyurethane resin, an acrylic urethane resin and the like can be given. Any of these may be used singly or in combination of two or more.

Examples of the colorant include inorganic pigments such as carbon black (black), iron black, titanium white, antimony white, chrome yellow, titanium yellow, red iron oxide, red cadmium, ultramarine blue and cobalt blue; Organic pigments or dyes such as quinacridone red, isoindolinone yellow and phthalocyanine blue; Metal pigments including flaky flakes such as aluminum and brass; (Pearl) pigment including flaky flakes such as titanium dioxide coated mica, basic carbonate flakes and the like are used.

When the ornamental layer has a pattern, it may be in the form of a wood, a marble pattern (for example, a travertine marble shape) or the like, a pattern in which a surface of a rock is imitated, , A tile attachment shape, and a brick laminated shape. There is also a shape such as a patchwork or a patchwork which is a combination of these. These shapes are formed by multicolor printing by the usual process colors of yellow, red, blue, and black, and multicolor printing by the characteristic color prepared by preparing individual color plates constituting a shape. In the present invention, since the texture (tactile feeling) can be expressed by a concave shape to be described later, a grain shape is suitable from the viewpoint of realistic texture.

The thickness of the decorative layer may be appropriately selected according to the desired pattern, and is usually about 1 to 20 mu m, preferably about 1 to 10 mu m.

[Resin Layer]

The resin layer in the decorative sheet of the present invention is preferably used in view of the protection of the decorative layer of the decorative sheet, the improvement of the molding processability by adjusting the total thickness of the decorative sheet, the tensile elastic modulus and the maximum point load, And is preferably a layer provided according to the purpose.

As the resin constituting the resin layer, an acrylic resin, a polycarbonate resin, a polyurethane resin, a polystyrene resin, a vinyl chloride resin, a vinyl acetate resin and the like are preferably used in addition to the polyester resin and the polyolefin resin used as the substrate sheet . From the viewpoints of improvement in molding processability and improvement in scratch resistance, polyester resins and polyolefin resins are preferable, and polyolefin resins are more preferable. From the same viewpoint, it is preferable that both the base sheet and the resin constituting the resin layer are polyolefin resins.

The resin layer may be provided between the substrate sheet and the surface protection layer. From the viewpoint of protecting the decorative layer, it is preferable that the resin layer is provided between the decorative layer and the surface protective layer.

The resin layer may be transparent or opaque. When the resin layer is provided between the decorative layer and the surface protection layer, it is preferable that the decorative layer is transparent in view of enabling the decorative layer to be seen more clearly. Here, transparent means not only colorless transparent but also colored transparent and translucent. When the resin layer is colored, the colorant to be used is preferably the same as the colorant used in the base sheet.

The thickness of the resin layer is preferably about 10 to 110 mu m, more preferably about 20 to 90 mu m, and even more preferably about 30 to 80 mu m. By setting the thickness of the resin layer within the above range, it is easy to adjust the total thickness of the decorative sheet to within the range specified in the present invention. Thus, the decorative layer of the decorative sheet is protected, The improvement in workability and the improvement in scratch resistance can be expected.

From the viewpoint of protecting the decorative layer and obtaining excellent scratch resistance, it is preferable to make the thickness of the resin layer thicker than that of the base sheet.

The resin layer can be subjected to a physical or chemical surface treatment such as an oxidation method or an unevenness method on one or both surfaces of the resin layer from the viewpoint of improving the adhesion with other layers constituting the decorative sheet of the present invention have. As the physical or chemical surface treatment, a method similar to the surface treatment of the substrate sheet is preferably exemplified.

[Surface protective layer]

The decorative sheet of the present invention has a surface protective layer for imparting surface characteristics such as scratch resistance, abrasion resistance, and chemical resistance. The surface protection layer is provided directly on the decorative layer, or is interposed between the other layers, for example, the resin layer. The surface protective layer is preferably formed by applying a resin composition containing a curable resin and curing the resin composition. By constituting the surface protective layer by the cured curable resin, the surface characteristics of the decorative sheet can be improved.

As the curable resin used for forming the surface protective layer, an ionizing radiation curable resin or the like is preferably used in addition to a thermosetting resin such as a two-part curable resin. The curable resin may be a so-called hybrid type in which a plurality of different kinds of resins are used. In this case, for example, an ionizing radiation curable resin and a thermosetting resin can be used in combination.

Among them, an ionizing radiation curable resin is preferable from the viewpoint of increasing the crosslinking density of the resin forming the surface protective layer and improving the scratch resistance or abrasion resistance of the surface. It is more preferable to use an electron beam-curable resin from the viewpoint that it can be applied without a solvent and is easy to handle.

(Ionizing radiation curable resin)

The ionizing radiation curable resin is a resin which has both of energy capable of crosslinking or polymerizing molecules in an electromagnetic wave or a charged particle beam, that is, crosslinking or curing by irradiation with ultraviolet rays or electron beams. Specifically, it can be appropriately selected from a polymerizable monomer, a polymerizable oligomer, and a prepolymer conventionally used as an ionizing radiation curable resin.

Typically, as the polymerizable monomer, a (meth) acrylate monomer having a radically polymerizable unsaturated group in the molecule is preferable, and among these, a polyfunctional (meth) acrylate is more preferable. In the present specification, the term " (meth) acrylate " means " acrylate or methacrylate " The polyfunctional (meth) acrylate may be any (meth) acrylate having two or more ethylenic unsaturated bonds in the molecule, and the number of ethylenically unsaturated bonds is not particularly limited. These polyfunctional (meth) acrylates may be used singly or in combination of two or more kinds.

Examples of the polymerizable oligomer include oligomers having radically polymerizable unsaturated groups in the molecule such as epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, Acrylate and the like.

Examples of the polymerizable oligomer include polybutadiene (meth) acrylate oligomer having high hydrophobicity and having a (meth) acrylate group in the side chain of the polybutadiene oligomer, silicone (meth) acrylate oligomer having polysiloxane bond in the main chain, An aminoplast resin (meth) acrylate oligomer modified with an aminoplast resin having a large number of reactive groups in a small molecule, a cationic oligomer having a cation in a molecule such as a novolak type epoxy resin, a bisphenol type epoxy resin, an aliphatic vinyl ether or an aromatic vinyl ether Oligomers having polymerizable functional groups, and the like.

In the present invention, a monofunctional (meth) acrylate may suitably be used in combination with the polyfunctional (meth) acrylate and the like within a range not to impair the object of the present invention for the purpose of lowering the viscosity of the same . These monofunctional (meth) acrylates may be used singly or in combination of two or more.

The thickness of the surface protective layer is preferably about 2 to 20 占 퐉, and more preferably about 2 to 10 占 퐉, from the viewpoint of obtaining excellent scratch resistance and durability, furthermore, surface characteristics such as abrasion resistance and chemical resistance.

The resin composition forming the surface protective layer may contain various additives other than the above insofar as the performance thereof is not impaired. Examples of the additive include a polymerization inhibitor, a crosslinking agent, an antistatic agent, an adhesion improver, an antioxidant, a leveling agent, a thixotropic agent, a coupling agent, a plasticizer, a defoaming agent, a filler and a solvent.

[Concave shape]

The surface protection layer has a concave shape. Since the decorative sheet of the present invention has a concave shape, the decorative sheet is particularly excellent in texture. This concave shape may be present at least in the surface protective layer. As the concave shape, for example, as shown in Fig. 1, it is possible to stay in the surface protective layer and reach the substrate sheet. It is preferable not only to stay in the surface protective layer but also to reach the resin layer, to reach the decorative layer, or to reach the substrate sheet from the viewpoint of obtaining excellent texture (touch).

The maximum depth of the concave shape should be 15 to 100%, preferably 15 탆 or more, with respect to the total thickness of the decorative sheet. By having such a maximum depth, it is possible to prevent the decorative sheet from being broken at the time of embossing, and to prevent the concave shape from becoming a broken finish. Thereby, excellent texture (touch) can be obtained, and as a result excellent designability can be obtained. From the same viewpoint, the maximum depth of the concave shape is preferably 15 to 80%, more preferably 25 to 80%. The lower limit of the maximum depth is preferably 20 占 퐉 or more, more preferably 30 占 퐉 or more. When the maximum depth of the concave shape is 100% with respect to the total thickness of the decorative sheet, the convex shape is revealed on the back side of the decorative sheet.

Here, the maximum depth of the concave shape is measured as follows. The height from the lowermost point of the concave shape to the surface of the surface protective layer was measured using a surface roughness shape measuring instrument with a cutoff value of 2.50 mm, a type of cutoff filter: 2RC, : Measured under straight line measurement conditions, and the deepest depth was defined as the maximum depth.

The method of performing concave processing on the surface protective layer is not particularly limited. For example, in consideration of easiness of working, emboss processing is preferably employed. The embossing may be carried out by a conventional method using a known sheet or embossing machine.

[Adhesive layer]

The decorative sheet of the present invention may have an adhesive layer as required. In particular, when the decorative sheet of the present invention has a resin layer, it is effective to form an adhesive layer when improving the adhesion between the resin layer and the decorative layer. As the adhesive constituting the adhesive layer, an adhesive commonly used in a decorative sheet can be used. The thickness of the adhesive layer is preferably about 0.1 to 50 mu m, and more preferably in the range of 1 to 30 mu m from the viewpoint of obtaining sufficient adhesiveness.

The adhesive is not particularly limited, and examples thereof include a polyurethane-based adhesive, an acrylic adhesive, an epoxy-based adhesive, and a rubber-based adhesive. Of these, a polyurethane-based adhesive is preferable from the viewpoint of adhesion and the like. As such a polyurethane-based adhesive, there is a two-part curing type urethane resin adhesive. The two-liquid curing type urethane resin adhesive is a two-component curing type urethane resin containing various hydroxyl group-containing compounds such as polyether polyol, polyester polyol and acryl polyol and various polyisocyanate compounds such as tolylene diisocyanate and hexamethylene diisocyanate .

In addition, acrylic-polyester-vinyl chloride vinyl acetate resin and the like are also suitable adhesives that easily exhibit adhesiveness by heating and can maintain the adhesive strength even in use at high temperatures.

The adhesive layer can be formed by a known layer forming method such as a coating method using an adhesive composition containing these resins and the like.

[Primer Layer]

The decorative sheet of the present invention may have a primer layer in any one of the layers in order to improve the interlayer adhesion, if necessary. Particularly, in the case of providing a layer other than the surface protective layer, for example, a resin layer, it is effective to form a primer layer between the surface protective layer and the resin layer from the viewpoint of obtaining excellent scratch resistance of the decorative sheet of the present invention .

The primer layer is a transparent or translucent layer. The primer layer can be formed of, for example, a binder resin similar to that used for the decorative layer described above. The thickness of the primer layer is preferably about 0.5 to 20 占 퐉, more preferably about 1 to 5 占 퐉.

[Production method of cosmetic sheet]

With respect to the method for producing a decorative sheet of the present invention, a decorative sheet having a base sheet, a decorative layer, a resin layer and a surface protective layer, which is one of preferable forms of the decorative sheet of the present invention, do. The decorative sheet of the present invention can be obtained by, for example, a step (1) of forming a decorative layer on a base sheet, a step (2) of providing a resin layer on the decorative layer, a curing resin composition being applied on the resin layer, And a step (3) of forming a surface protective layer in this order.

First, step (1) is a step of forming a decorative layer on a base sheet. The decorative layer is formed by applying the ink used for the decorative layer on the substrate sheet to form a desired coloring layer or a pattern layer. The application of the ink can be carried out by a known method such as a gravure printing method, a bar coating method, a roll coating method, a reverse roll coating method, and a comma coating method. Preferably, the ink is applied by a gravure printing method.

Further, in the case of performing the surface treatment on the substrate sheet, the surface treatment can be performed before applying the ink used for the decorative layer. As the surface treatment, a primer layer may be formed on the surface or backside of the substrate sheet. When the primer layer is provided between the surface of the base sheet, that is, between the base sheet and the decorative layer, the ink used for the decorative layer may be provided before application. In the case of providing the backing primer layer on the back surface of the substrate sheet, that is, the surface opposite to the surface on which the decorative layer is formed, the back primer layer may be provided before the ink used for the decorative layer is applied, You can also install it. Formation of the primer layer can be performed by applying the resin composition forming the primer layer by a known method such as gravure printing, bar coating, roll coating, reverse roll coating, or comma coating.

Step (2) is a step of providing a resin layer on the decorative layer. The resin layer can be formed using a resin composition which forms a resin layer after applying an adhesive to the substrate sheet having the decorative layer as necessary. Specifically, the resin layer can be adhered or pressed onto the decorative layer by a method such as extrusion lamination, dry lamination, wet lamination, thermal lamination and the like.

Step (3) is a step of applying a curable resin composition on the resin layer and curing the surface protective layer to form a surface protective layer. The surface protective layer is obtained by applying an ionizing radiation curable resin composition comprising the above ionizing radiation curable resin onto a resin layer or a primer layer provided according to purpose on the resin layer and curing.

The application of the resin composition for forming the surface protective layer is carried out by a known method such as gravure coat, bar coat, roll coat, reverse roll coat or comma coat so that the thickness after curing is usually about 1 to 20 mu m . Of these methods, a gravure coat is preferred.

When an ionizing radiation-sensitive resin composition is used to form the surface protective layer, the uncured resin layer formed by applying the resin composition is irradiated with ionizing radiation such as electron beams or ultraviolet rays to crosslink and cure the surface protective layer. Here, when an electron beam is used as the ionizing radiation, the acceleration voltage can be appropriately selected in accordance with the thickness of the resin or layer to be used. It is preferable to cure the uncured resin layer at an acceleration voltage of about 70 to 300 kV.

The irradiation dose is preferably such that the crosslinking density of the ionizing radiation curable resin is saturated. The irradiation dose is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad).

The electron beam source is not particularly limited and various electron beam accelerators such as, for example, a Cocraft Walton type, a Bandegraft type, a resonant transformer type, an insulating core transformer type, or a linear type, a dinamitron type and a high frequency type can be used.

When ultraviolet rays are used as the ionizing radiation, those containing ultraviolet rays having a wavelength of 190 to 380 nm are emitted. The ultraviolet light source is not particularly limited, and for example, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a carbon arc, or the like is used.

When a thermosetting resin composition is used to form the surface protective layer, a heat treatment according to the resin composition to be used may be performed and cured to form a surface protective layer.

The decorative sheet of the present invention is a decorative sheet having designability including excellent appearance and texture (touch) including excellent finish and good molding processability in response to a demand for thinning. Especially, since it has excellent heat characteristics and mechanical characteristics (strength), it is used in processing such as laminating, lapping, and vacuum forming, which is exposed to a harsh environment such as a thermal environment or a vacuum environment, Peeling of the decorative sheet and no creasing, bursting or wrinkling of the decorative sheet can be achieved, and excellent molding processability can be obtained. As a result, excellent designability can be obtained when the decorative sheet is adhered to a member. Therefore, the decorative sheet of the present invention is suitably used for laminating, lapping, or vacuum forming.

[Facial member]

The decorative member of the present invention is obtained by bonding the decorative sheet of the present invention to a member (adherend) by processing such as laminating, lapping, or vacuum molding, and performing finish processing as required, The surface of the decorative sheet on the base sheet side and the adherend are adhered with the adhesive layer interposed therebetween.

As the adherend, plate materials such as flat plates and curved plates of various materials; Dimensional article, sheet (or film), and the like. Examples of the plate material include plate materials such as wood veneer sheets such as wood veneer, wood veneer, particle board and MDF (medium density fiber board); Plate materials such as iron and aluminum; Ceramics such as glass and ceramics, non-cemented materials such as gypsum, and non-ceramic materials such as ALC (lightweight foamed concrete); (Acrylonitrile-butadiene-styrene copolymer) resin, a phenol resin, a vinyl chloride resin, a cellulose resin, a rubber and the like, such as a polyolefin resin such as an acrylic resin, a polyester resin, a polystyrene resin and a polypropylene . Examples of the material of the three-dimensional shaped article or sheet include the same wood-based plate materials as those described above, the same metal materials as those described above, the same industrial materials as those described above, and the same resin materials as described above.

The adhesive used for the adhesive layer for adhering the decorative sheet to the adherend is not particularly limited and a known adhesive may be used. As the adhesive, for example, a heat-sensitive adhesive, a pressure-sensitive adhesive and the like are preferably used. As the resin used for the adhesive constituting the adhesive layer, for example, an acrylic resin, a polyurethane resin, a vinyl chloride resin, a vinyl acetate resin, a vinyl chloride-vinyl acetate copolymer resin, a styrene-acrylic copolymer resin, Based resin and a polyamide-based resin are used. Further, a two-liquid curing type polyurethane adhesive or polyester adhesive using isocyanate or the like as a curing agent can also be applied.

Further, a pressure-sensitive adhesive may be used for the adhesive layer. As the pressure-sensitive adhesive, a pressure-sensitive adhesive such as an acrylic type, a urethane type, a silicone type or a rubber type can be suitably selected and used.

The adhesive layer can be formed by coating the resin with a solution, an emulsion or the like in a form capable of being applied by a means such as a gravure printing method, a screen printing method, or a reverse coating method using a gravure plate, and drying.

The thickness of the adhesive layer is not particularly limited and is preferably about 1 to 100 mu m. By setting this range, excellent adhesion can be obtained.

As a method for bonding the decorative sheet and the adherend, for example, a lamination method in which an adherent is interposed therebetween to press a plate-shaped adherend with a pressure roller to laminate the adherend; A lapping process in which a decorative sheet is successively pressed and adhered to a plurality of side faces constituting an adherend by different rollers in a plurality of directions while supplying an adhesive agent between the decorative sheets; The silicone rubber sheet is heated by the heater until the predetermined temperature at which the decorative sheet fixed to the stationary frame softens, and the vacuum-formed metal mold is pressed against the softened decorative sheet by heating, and at the same time, A vacuum forming process in which the air is sucked and the decorative sheet is tightly adhered to the vacuum forming die.

In the case of using a hot melt adhesive (heat-sensitive adhesive) in the laminating or lapping process, the heating temperature varies depending on the type of the resin constituting the adhesive, and is usually about 160 to 200 占 폚. In the case of a reactive hot melt adhesive, the heating temperature is about 100 to 130 占 폚. The vacuum forming process is generally carried out while heating, and the heating temperature is usually about 80 to 130 占 폚, and preferably about 90 to 120 占 폚.

The decorative member obtained as described above can be cut at an arbitrary position and arbitrary decoration such as grooving and chamfering can be performed on the surface or the cut part of the wood using a cutting machine such as a router or a cutter. And for various applications such as walls, ceilings and floors; Window frames, doors, railings, baseboards, spears, malls, etc.; Surface planks of cabinets such as kitchens, furniture, pharmacy electric appliances, and office automation equipment; It can be used for interior or exterior of vehicles.

Example

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited in any way by this example.

(Assessment Methods)

(1) Processing suitability (Wrapping property)

The condition of the makeup members obtained in each of the Examples and Comparative Examples was visually observed and evaluated according to the following criteria.

A: No change in appearance was observed.

B: Extension between the adherend and the decorative sheet was confirmed.

C: Springback occurred in which the decorative sheet was peeled off from the adherend, or could not be wrapped (could not be adhered).

(2) Machinability (machinability)

The decorative members obtained in each of the examples and the comparative examples were cut using a router and the state of the finished surface after cutting was visually observed and evaluated according to the following criteria.

A: Almost no change in appearance was observed.

B: Projections, recesses, dropouts and the like are slightly generated, but there is no practical problem.

C: Many protrusions or recesses, dropouts, etc. occurred.

(3) Designability

The appearance (concave shape) of the cosmetic material obtained in each of the Examples and Comparative Examples was visually observed and evaluated according to the following criteria.

A: The concave shape remained, and the texture (touch) was abundant, and the designability was excellent.

B: There was a part where the concave shape was slightly shallow, but there was texture (touch), and it had a design without problem in practical use.

B-: Although there is a portion where the concave shape becomes shallow, the texture (touch) remains, and it has designability without problem in practical use.

C: The concave shape is entirely shallow or disappears, and the texture is lost.

(4) Scratch resistance

A pencil scratch coating film hardness tester ("PSH540-40IP (model number)" manufactured by Toyo Seiki Seisakusho Co., Ltd.) was used for the decorative members obtained in each of the examples and the comparative examples, and in accordance with JIS K5600-5-4, Pencil Scratching Value A pencil hardness test was conducted using a pencil for testing (manufactured by Mitsubishi Enpitsu Kabushiki Kaisha) and evaluated according to the following criteria.

A: The pencil hardness at break of the decorative sheet was not less than HB.

B: The pencil hardness at which the tearing of the decorative sheet occurred was from 3B to B.

C: The pencil hardness at which tearing of the decorative sheet occurred was 4B or less.

Example 1

A printing ink in which a polypropylene resin sheet (thickness: 50 占 퐉) subjected to double-sided corona discharge treatment was used as a base sheet and a two-liquid curing type acrylic-urethane resin as a binder was applied to one side of the base sheet by gravure printing, (Thickness: 2 mu m) was provided on the other side of the substrate, and a two-liquid curing type urethane-rich mixed resin composition was applied on the other side to form a backing primer layer (thickness: 2 mu m). A transparent polyurethane resin adhesive was applied on the decorative layer to form an adhesive layer (thickness after drying: 3 mu m), and the transparent polypropylene resin was heated and melt extruded by a T-die extruder to obtain a thickness (Thickness: 19 mu m) so as to have a thickness of 80 mu m.

Subsequently, a corona discharge treatment was applied to the surface of the resin layer, and then a two-liquid curing type acryl-urethane resin composition was applied by gravure printing to form a primer layer (thickness after drying: 1 m) (Solid content: 3 g / m < 2 >) by a roll coating method and dried to form an uncured resin layer. Under the environment of an oxygen concentration of 200 ppm, electron beams (pressurizing voltage: 125 KeV, 5Mrad) to cure the uncured resin layer to obtain a surface protective layer (thickness: 3 mu m). Thereafter, emboss processing was performed from the side of the surface protective layer to form a concave-convex shape having a concave shape with a maximum depth of 50 mu m in the form of a wooden conduit to obtain the decorative sheet of Example 1. [

An adhesive layer (having a thickness of 20 mu m) was formed by applying a polyurethane based thermal adhesive (hot melt adhesive, " PUR704 (model number) ", manufactured by Clive Care Japan) to the backside primer layer side of the obtained decorative sheet, The decorative sheet and the decorative sheet were adhered to each other so as to follow the shape of the adhering member made of polyvinyl chloride in the section L shape before the decorative sheet was solidified. The above-obtained decorative member was subjected to the above evaluation, and the evaluation results thereof are shown in Table 1.

Examples 2 to 10

Except that the thickness of the resin layer in Example 1 was changed to give the total thickness of the decorative sheet shown in Table 1 and the material of the base sheet was changed to the ratio of the tensile elastic modulus shown in Table 1 or the ratio of the maximum point load, The decorative sheets of Examples 2 to 10 and the decorative members using the decorative sheets were produced in the same manner as in Example 1. [ The above-obtained decorative member was subjected to the above evaluation, and the evaluation results thereof are shown in Table 1.

Example 11

The procedure of Example 1 was repeated except that the substrate sheet (thickness: 70 占 퐉) containing polyethylene terephthalate resin was used as the substrate sheet, and the adhesive layer and the resin layer were not provided. And a decorative member made of the decorative sheet. The above-obtained decorative member was subjected to the above evaluation, and the evaluation results thereof are shown in Table 1.

Comparative Examples 1 to 6

Except that the thickness of the resin layer in Example 1 was changed to the total thickness of the decorative sheet shown in Table 1 or the base sheet was changed to the ratio of the tensile elastic modulus shown in Table 1 or the maximum point load ratio, 1, a decorative sheet of each of Comparative Examples 1 to 6 and a decorative member using the decorative sheet were produced. The above-obtained decorative member was subjected to the above evaluation, and the evaluation results thereof are shown in Table 1.

Comparative Example 7

A decorative sheet of Comparative Example 7 was obtained in the same manner as in Example 11 except that the polyethylene terephthalate resin forming the substrate sheet in Example 11 was changed to a decorative sheet having a maximum point load ratio shown in Table 1, And a makeup member using the makeup sheet was produced. The above-obtained decorative member was subjected to the above evaluation, and the evaluation results thereof are shown in Table 1.

The decorative sheet of the present invention is a decorative sheet having designability including excellent appearance, texture (touch), and the like, which has excellent molding processability in correspondence with a demand for thinning. Particularly, since it has excellent heat characteristics and mechanical properties (strength), excellent molding processability can be obtained even in the case of being exposed to a heating environment such as a lamination process, a lapping process, a vacuum forming process, or a harsh environment such as a vacuum environment, As a result, excellent designability can be obtained when bonded to members. Taking these characteristics into consideration, the decorative sheet of the present invention can be used for various applications, for example, interior and exterior members of buildings such as walls, ceilings, floors and the like; Window frames, doors, railings, baseboards, spears, malls, etc.; Surface planks of cabinets such as kitchens, furniture, pharmacy electric appliances, and office automation equipment; It can be suitably used for interior decoration and exterior of a vehicle.

1: Facial sheet
2: substrate sheet
3: decorative floor
4: Resin layer
5: Adhesive layer
6: Surface protective layer
7: concave shape

Claims (8)

Wherein a decorative layer and a surface protective layer are provided in this order on a base sheet made of a polyester resin or a polyolefin resin and the total thickness is 70 to 135 占 퐉 and at least the surface protective layer has a concave shape, And the ratio of the tensile elastic modulus at 120 占 폚 and 20 占 폚 is 1:12 to 1: 160, and at 120 占 폚 and 20 占 폚, the maximum depth is 15 to 100% Wherein the ratio of the maximum point load at 30 mm stretching is 1: 1.7 to 1:30. The method according to claim 1,
Further comprising a resin layer between the substrate sheet and the surface protection layer. 3. The method according to claim 1 or 2,
Wherein the base sheet is composed of a polyolefin resin. 3. The method of claim 2,
Wherein the resin layer is composed of a polyolefin resin. The method according to any one of claims 1, 2, and 4,
Wherein the surface protection layer is a cured product of an ionizing radiation curable resin composition. The method according to claim 2 or 4,
A base sheet, a decorative layer, a resin layer and a surface protective layer in this order, and the resin layer and the surface protective layer are transparent. The method according to any one of claims 1, 2, and 4,
A decorative sheet used for laminating or lapping. A decorative member comprising a base sheet side surface and an adherend of the decorative sheet according to any one of claims 1, 2, and 4 adhered via an adhesive layer.

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